JP5213373B2 - Process for preparing pigments - Google Patents

Description

  The present invention relates to pigments that act as melamine hosts, methods for preparing their hydrates, and the use of products of these methods.

  It is known that there are significant variations in product properties in the preparation of nickel azobarbiturate complexes containing melamine as a guest and their hydrates. Certain parameters of the resulting material, such as the BET specific surface area, are subject to more or less significant fluctuations, especially under manufacturing conditions on an industrial scale, especially in batch processes. Of course, this is a drawback, and consumers of these products require a constant product quality.

  For example, as described in (Patent Document 1) or (Patent Document 2), a certain standardization (reproducibility) of product quality is possible by the heat treatment process. Of course, especially on an industrial scale, this means additional, time-consuming processes and therefore increased production costs.

Similarly, (Patent Document 3) describes a large quality fluctuation in the batch production of Ni complexes according to the prior art, and proposes to avoid this drawback by special addition in the synthesis stage. This, of course, requires additional logistics strategic efforts and costs and affects the composition of the product as some or all of these additions are incorporated as guests in the Ni complex instead of melamine.
EP-A1-0994162 DE 10328999A1 EP-A 1612246

  Surprisingly now, the quality and reproducibility of azobarbituric acid nickel complexes containing melamine as a guest are It has been found that it is significantly improved by reacting with the compound and melamine. By the method of the invention, even industrially, compounds of formula (I) containing melamine as a guest have a manageable surface area, vivid color density and a very narrow particle size distribution. Can be prepared with good reproducibility. This is particularly advantageous for the production of stable dispersions with low viscosity.

  Accordingly, the present invention comprises a compound of formula (I) comprising melamine as a guest

またはその互変異性体構造およびそれらの水和物の顔料を調製する方法であって、式（ＩＩ）のモノ−塩および式（ＩＩＩ）のジ−塩

Or a process for preparing pigments of tautomeric structures and hydrates thereof, comprising a mono-salt of formula (II) and a di-salt of formula (III)

［式中、カチオン１、カチオン２およびカチオン３は、互いに独立して、任意の所望の一価のカチオン（Ｈは除く）であるか、または１個の正電荷に対応する任意の所望の多価カチオンの一部分である］
の混合物、をニッケル化合物およびメラミンと反応させることを特徴とする方法を提供する。

[Wherein cation 1, cation 2 and cation 3 are, independently of one another, any desired monovalent cation (excluding H) or any desired multiple corresponding to one positive charge. Part of a valent cation]
And a melamine compound is reacted with a nickel compound and melamine.

  Compound (I) may comprise not only melamine but, where appropriate, further guest compounds of the type described, for example, in EP 0994162 (part 5, page 40 to page 7, line 58). Compound (I) preferably has two guest melamine units.

  As mono-salts of the formula (II) it is preferred to use lithium salts, sodium salts, potassium salts, magnesium salts, calcium salts, aluminum salts or ammonium salts, in particular azobarbituric acid mono-potassium salts, of the formula (III) As the di-salt, lithium salt, sodium salt, potassium salt, magnesium salt, calcium salt, aluminum salt or ammonium salt or, where appropriate, mixed salts thereof, in particular azobarbituric acid di-potassium salt should be used. Is preferred.

The azobarbituric acid mono-potassium salt of formula (II) in which cation 1 represents K ⁺ and the azobarbituric acid di-potassium salt of formula (III) in which cation 2 and cation 3 each represent K ⁺ are EP-A 1086992 Is known by. EP-A 1086992 also describes a process for preparing compound (I), but from mono- or di-salts by reaction with nickel compounds and melamine. The pigments of formula (I) prepared by the method disclosed in EP 1086992 are already useful pigments.

  Particularly preferably, cation 1, cation 2 and cation 3 in formulas II and III are, independently of one another, alkali metal cations, in particular lithium cation, sodium cation or potassium cation, 1/2 alkaline earth metal cation, in particular 1 / 2 magnesium cation, 1/2 calcium cation, 1/3 aluminum cation, or an ammonium cation, in particular an unsubstituted ammonium cation, which is unsubstituted or substituted by any desired radical.

  Preferably, this mixture is 5 to 80 mol%, in particular 10 to 60 mol%, particularly preferably 10 to 40 mol% of the di-salt of formula II, based on the total amount of mono-salts and di-salts of formula II and formula III. including.

Particularly preferably, cation 1, cation 2 and cation 3 are each K ⁺ .

  The mixture of mono-salt II and di-salt III preferably starts from mono-salt II, directly from an azobarbituric acid monocation complex, for example in the form of a solution or as a solid, such as a cation compound such as an oxide (oxidation). Product), hydroxide (hydroxide), carbonate (carbonate), phosphate (phosphate), hydrogen phosphate (hydrogen phosphate), acetate, especially alkali metal hydroxide, trialkal Produced by adding metal phosphate or dialkali metal hydrogen phosphate. Particular preference is given to the addition of basic potassium compounds, in particular potassium hydroxide, tripotassium phosphate or dipotassium hydrogen phosphate, for example in the form of solutions or else as solids.

  Preferably, the mixture of mono-salt II and di-salt III is reacted in a water system at a temperature of 70-100 ° C. with a nickel salt and melamine to give compound (I).

  In the reaction with the nickel salt, the pH is preferably lower than pH 3, in particular to the level of pH 1 to pH 2.

  Preferably, the reaction to compound (I) is completed by subsequent stirring for 1-3 hours, in particular at a temperature between 90 ° C. and 100 ° C.

  Particularly preferably, a mixture of mono-salt II and di-salt III, in which cation 1, cation 2 and cation 3 are in each case potassium, is reacted first with a nickel salt and then with melamine.

  The pigments obtained by the process of the invention can of course be post-treated by a heat treatment step of the kind described, for example, in EP A1-0994162 or DE 10328999A1. However, advantageously, this aftertreatment can also be omitted completely.

  The suspension obtained in this preparation is preferably filtered and the resulting press cake can be dried, if appropriate after washing with water.

  On the other hand, in this context, ordinary drying methods such as paddle drying are preferred. Powder pigments are obtained using this type of drying method and subsequent conventional grinding methods for pigments.

  The press cake is preferably spray dried as an aqueous slurry. The slurry for the spray process preferably has a solid content of 10% to 40% by weight, in particular 15% to 30% by weight.

Preferred pigments prepared by the process of the present invention is greater than 100 m ² / g, preferably greater than 110m ² / g, in particular of 115~150m ² / g, as measured in accordance with DIN 66131, it has a BET surface area.

  Furthermore, the present invention provides a method for producing a pigment preparation, wherein at least one pigment prepared according to the present invention and at least one dispersant are mixed. Such pigment preparations are also inventive. These pigment preparations preferably serve to aid in aqueous incorporation.

  For suitable dispersants, reference may be made to the prior art, in particular EP-A1-0994164, page 8, line 56 to page 11, line 23, whose disclosure is part of the present application.

  The present invention further provides a photoresist comprising at least one photocurable monomer, at least one photoinitiator, and at least one pigment prepared by the method of the present invention. The present invention further provides color filters and liquid crystal displays produced therefrom comprising at least one pigment prepared by the method of the present invention.

  In the case of the production of color filters for liquid crystal displays, the pigments prepared according to the invention are ground, preferably in an organic solvent, if appropriate with the addition of binder resins and / or dispersants, and then light A curable monomer, a photoinitiator, and, if appropriate, further binders and / or solvents are added to process the photoresist. The photoresist is then applied to a suitable substrate, typically a glass plate, by a suitable coating technique such as, for example, roller coating, spray coating, spin coating, dip coating or air knife coating. The coated plate is then exposed using a photomask, then cured and developed to obtain a finished color filter.

  The present invention further preferably provides the use of a pigment prepared according to the present invention as a pigment for a color filter of a liquid crystal display.

  The compounds (I) or pigment preparations prepared according to the invention containing melamine as a guest are furthermore significantly suitable for all pigment applications.

  These are, for example, for all types of pigment varnishes, for the production of printing colorants, distemper colorants or binder colorants, synthetic, semi-synthetic or natural polymer compounds such as polyvinyl chloride, polystyrene, polyamide, polyethylene or Suitable for raw material coloring such as polypropylene. They can also be used for spin-dyeing of natural, regenerated or synthetic fibers such as cellulose, polyester, polycarbonate, polyacrylonitrile or polyamide fibers, and also for printing textiles and paper. These pigments can be used for coloring paper, textile printing by grinding or kneading in the presence of finely divided, stable aqueous pigmentation of emulsions and nonionic, anionic or cationic surfactants. The present invention provides a paint colorant useful for laminate printing or dyeing viscose raw yarn. The pigments prepared by the method of the present invention are very suitable for inkjet applications and color filters for liquid crystal displays.

[Example]
[Mono potassium salt]
The starting material for the process of the present invention is Example 1 of EP-A 1086992, ie α-form azobarbituric acid monopotassium salt · 1H ₂ O, which is described below.

  136 g of aminoguanidine hydrogen carbonate is placed in 810 g of distilled water and dissolved therein with 280 g of hydrochloric acid (concentration 30%). The solution is then cooled to about −10 ° C. with 780 g of ice and subsequently mixed with 232 g of a 37% strength aqueous potassium nitrite solution to about 15 ° C. This is followed by stirring at about 15 ° C. for 15 minutes, after which 2.0 g amidosulfuric acid is added. Then 269 g of barbituric acid are added and the mixture is subsequently heated to 55 ° C. and stirred for 2 hours. The mixture is then adjusted to pH 2.5 with aqueous potassium hydroxide and stirred for 30 minutes. Thereafter, the pH is adjusted to 4.8 using an aqueous potassium hydroxide solution, and then stirring is continued for 30 minutes. Subsequently, the batch is heated to 80 ° C. and stirred at pH 4.8 for 3 hours. The product is then isolated with a suction filter and washed until no electrolyte is present.

[Comparative example not according to the present invention]
EP-A 1086992 prepared according to Example 1 and corresponding to 425 g of α-form azobarbituric acid monopotassium salt 1H ₂ O moistened with water and having a solids content of 40%, 170 g (0.5 mol) dry Is stirred in 5000 ml of distilled water using a laboratory stirrer and heated to 95 ° C. Add 1,060 g of a 6.5% strength aqueous nickel chloride solution over 30 minutes. Thereafter, 126 g (1 mol) of melamine is added and stirring is continued at 95 ° C. for 1.5 hours. The pH is then adjusted to 5.5 using potassium hydroxide solution. The product is then isolated with a suction filter, washed until free of electrolyte, dried at 80 ° C. in a vacuum drying cabinet and ground.

  The specific surface area is determined according to DIN 66131: Determination of the specific surface area of a solid by gas adsorption by the method of Brunauer, Emmett and Teller (BET).

This product has a BET surface area of 83 m ² / g.

In repeated synthesis, considerable variation ^{(57m 2 / g~92m 2 / g} ) can be seen.

[Example 1 according to the present invention]
Distilled water prepared according to Example 1 of EP 1086992, 425 g of α-form azobarbituric acid monopotassium salt 1H ₂ O moistened with water of 40% solid content, equivalent to 170 g (0.5 mol) when dried Stir with a laboratory stirrer in 5000 ml and heat to 95 ° C.

  42 g of 10% strength potassium hydroxide solution are added dropwise (0.075 mol; 15% based on the azobarbituric acid monopotassium salt used) and the mixture is stirred for 30 minutes. This gives a mixture in a molar ratio of 85 parts monopotassium salt and 15 parts dipotassium salt. Add 1060 g of a 6.5% strength aqueous nickel chloride solution over 30 minutes. Thereafter, 126 g (1 mol) of melamine is added and stirring is continued at 95 ° C. for 1.5 hours. The pH is then adjusted to 5.5 using potassium hydroxide solution. Subsequently, the product is isolated with a suction filter, washed until free of electrolyte, dried at 80 ° C. in a vacuum drying cabinet and ground.

  The specific surface area is determined according to DIN 66131: Determination of the specific surface area of a solid by gas adsorption according to the method of Brunauer, Emmet and Teller (BET).

This product has a BET surface area of 129 m ² / g.

The repetitive synthesis, a slight variation ^{(121m 2 / g~134m 2 / g} ) not Shikami be.

[Example 2 according to the present invention]
The reaction is carried out in the same manner as in Example 1 except that 28 g of 10% strength potassium hydroxide solution is added dropwise (0.05 mol; 10% based on the monopotassium azobarbituric acid used). This gives a mixture in a molar ratio of 90 parts monopotassium salt and 10 parts dipotassium salt.

This product has a BET surface area of 126 m ² / g.

Repeat the synthesis, a slight variation ^{(120m 2 / g~135m 2 / g} ) not Shikami be.

[Example 3 according to the present invention]
The reaction is carried out in the same manner as in Example 1 except that 56 g of 10% strength potassium hydroxide solution is added dropwise (0.1 mol; 20% based on the monopotassium azobarbituric acid used). This gives a mixture with a molar ratio of 80 parts monopotassium salt and 20 parts dipotassium salt.

This product has a BET surface area of 131 m ² / g.

The repetitive synthesis, a slight variation ^{(126m 2 / g~135m 2 / g} ) not Shikami be.

[Embodiment 4 of the present invention]
The reaction is carried out in the same manner as in Example 1 except that 84 g of a 10% strength potassium hydroxide solution is added dropwise (0.15 mol; 30% based on the monopotassium azobarbituric acid used). This gives a mixture in a molar ratio of 70 parts monopotassium salt and 30 parts dipotassium salt.

This product has a BET surface area of 131 m ² / g.

The repetitive synthesis, a slight variation ^{(131m 2 / g~144m 2 / g} ) not Shikami be.

[Example 5 according to the present invention]
The reaction is carried out as in Example 1, except that 21.2 g of tripotassium phosphate are added (0.10 mol; 20% based on the azobarbituric acid monopotassium salt used). Tripotassium phosphate converts 2 units of azobarbituric acid monopotassium salt to azobarbituric acid dipotassium salt and in the process becomes dihydrogen phosphate.

  This gives a mixture in a molar ratio of 60 parts monopotassium salt and 40 parts dipotassium salt.

This product has a BET surface area of 143 m ² / g.

[Example 6 of the present invention]
The reaction is carried out in the same manner as in Example 1 except that 17.4 g of dipotassium hydrogen phosphate is added (0.10 mol; 20% based on the azobarbituric acid monopotassium salt used). Dipotassium hydrogen phosphate converted 1 unit of azobarbituric acid monopotassium salt to azobarbituric acid dipotassium salt and in the process became dihydrogen phosphate.

  This gives a mixture with a molar ratio of 80 parts monopotassium salt and 20 parts dipotassium salt.

This product has a BET surface area of 124 m ² / g.

Claims (5)

Formula (I) with melamine as guest

Or a tautomer structure thereof and a method for producing pigments of these hydrates,
Azobarbituric acid mono-cationic salt (II) and azobarbituric acid di-cationic salt (III)

Wherein the cation 1, cation and cation3 independently of one another, are selected from lithium, potassium, and from the group consisting of ammonium cation. ]
Production method of a mixture of which comprises reacting a nickel compound and melamine. Synthesis, for mass coloration of semisynthetic or natural polymer compounds, and natural, for yarn dyeing reproduction or artificial textiles, and also, printing colorants for textile and paper printing, Disperse A method for producing a temper colorant or a binder colorant, wherein the pigment is produced according to the method according to claim 1 and further using the pigment. A method for producing a colorant. Method for producing a pigment preparation comprising the steps of producing at least one pigment according to the method described, the step of mixing at least one dispersant the pigment in claim 1. At least one pigment, and at least one photoinitiator, a manufacturing method of a photoresist containing a photocurable monomer, a process for producing a pigment according to the method described in claim 1, then the pigment A photoresist comprising a step of grinding, and further comprising adding at least one photoinitiator and a photocuring monomer to the ground pigment, and optionally adding or not adding a binder and / or solvent. Manufacturing method . The following steps:
Producing a photoresist according to the method of claim 4;
Applying the photoresist to a substrate to produce a coated plate; and
Exposing the coated plate using a photomask and then curing and developing;
A method for producing a color filter , comprising: